The present invention relates to a photographic element and a silver halide photographic light sensitive material (hereinafter, also denoted simply as a photographic material) and in particular to a photographic element and a silver halide photographic material exhibiting improved color reproducibility, specifically, expanded color gamut of obtained dye images and enhanced suitability for a light source used for visual appreciation of dye images.
Recently, various color imaging systems have become popular, including a silver halide photographic system, electrophotography, ink-jet printing and thermal transfer recording. Consumers demands for image qualities of silver halide photographic materials superior in productivity to other imaging systems have increased from year to year. Demand for high image quality include improvements in color reproduction, tone reproduction and sharpness. Specifically, with regard to color reproduction, there have been studies on improvements in spectral absorption characteristics of yellow, magenta and cyan dyes.
In the conventional design of spectral absorption characteristic of dyes, it was common to allow yellow dyes to have an absorption maximum in the vicinity of 450 nm, magenta dyes to have an absorption maximum in the vicinity of 550 nm and cyan dyes to have an absorption maximum in the vicinity of 650 nm. Thus, it was a general practice to maintain the difference in xcexmax between respective dyes to be an extent of 100 nm. Thereby, preferable yellow, magenta and cyan colors were maintained and shifting this balance to a larger extent was shown to cause failure in color. Recently, however, it was also proved that only such design philosophy was insufficient to achieve satisfactory color reproduction and there have been attempted various designs.
JP-A No. 63-153546 (hereinafter, the term, JP-A refers to an unexamined, published Japanese Patent Application) proposed a technique for controlling wavelengths of absorption maximums (xcexmax) of yellow, magenta and cyan dyes to expand the color gamut of obtained dye images and to minimize dependency on light sources used for visual appreciation of dye images. Thus, it was described in this disclosure that the spectral absorption band of the magenta dye was narrowed and the wavelength of the absorption maximum of the dye was fixed within an intended region. However, it was proved that when using a pyrazoloazole type magenta coupler satisfying the spectral absorption maximum taught in this disclosure, appearance of gray images were markedly varied under different light sources, i.e., dependence on a light source for visual appreciation was increased.
It is generally known that narrowing the spectral absorption band of an individual dye is advantageous to expand the color gamut but it also disadvantageously results in an increase of dependency on light sources for visual appreciation. It has therefore been considered to satisfy both criteria.
JP-A No. 10-83046 proposed a technique, in which narrowing an absorption band of a cyan dye was achieved by the use of a specified cyan coupler, thereby leading to expanded color gamut. However, it was proved that a balance of spectral absorptions of yellow, magenta and cyan dyes was not taken into account so that this technique was insufficient to achieve desired improvements.
In view of the foregoing, accordingly, it is an object of the present invention to provide a photographic element and a silver halide photographic material, which are superior in color reproduction, specifically in color gamut and suitability for a light source used in visual appreciation.
The foregoing object of the invention can be accomplished by the following photographic element and silver halide photographic material:
(1) A photographic element comprising a yellow dye forming coupler, a magenta dye forming coupler and a cyan dye forming coupler, wherein spectral reflection absorption characteristics of a yellow dye, a magenta dye and a cyan dye which are formed of the yellow dye forming coupler, the magenta dye forming coupler and the cyan dye forming coupler, respectively, meet the following requirements:
110xe2x89xa7xcexmax(M)xe2x88x92xcexmax(Y)xe2x89xa795,
80xe2x89xa7xcexmax(C)xe2x88x92xcexmax(M)xe2x89xa770,
xe2x80x830.43xe2x89xa7Abs600(M)xe2x89xa70.38,
and
0.48xe2x89xa7Abs550(C)xe2x89xa70.35,
wherein xcexmax(Y) is a wavelength at an absorption maximum of the formed yellow dye, xcexmax(M) is a wavelength at an absorption maximum of the formed magenta dye and xcexmax(C) is a wavelength at an absorption maximum of the formed cyan dye; Abs600 (M) is an absorbance at a wavelength of 600 nm of the magenta dye having 1.0 of an absorbance at the absorption maximum and Abs550 (C) is an absorbance at a wavelength of 550 nm of the cyan dye having 1.0 of an absorbance at the absorption maximum;
(2) A photographic element comprising a yellow dye forming coupler, a magenta dye forming coupler and a cyan dye forming coupler, wherein spectral reflection absorption characteristics of a yellow dye, a magenta dye and a cyan dye which are formed of the yellow dye forming coupler, the magenta dye forming coupler and the cyan dye forming coupler, respectively, meet the following requirements:
108xe2x89xa7xcexmax(M)xe2x88x92xcexmax(Y)xe2x89xa7100,
80xe2x89xa7xcexmax(C)xe2x88x92xcexmax(M)xe2x89xa770,
0.42xe2x89xa7Abs600(M)xe2x89xa70.40,
and
0.46xe2x89xa7Abs550(C)xe2x89xa70.35,
wherein xcexmax(Y) is a wavelength at an absorption maximum of the formed yellow dye, xcexmax(M) is a wavelength at an absorption maximum of the formed magenta dye and xcexmax(C) is a wavelength at an absorption maximum of the formed cyan dye; Abs600 (M) is an absorbance at a wavelength of 600 nm of the magenta dye having 1.0 of an absorbance at the absorption maximum and Abs550 (C) is an absorbance at a wavelength of 550 nm of the cyan dye having 1.0 of an absorbance at the absorption maximum;
(3) A reflection-type or transmission-type silver halide photographic light sensitive material comprising on a refection or transmission support a blue-sensitive silver halide emulsion layer containing a yellow dye forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye forming coupler and a red-sensitive silver halide emulsion layer containing a cyan dye forming coupler, wherein spectral reflection absorption characteristics of a yellow dye, a magenta dye and a cyan dye which are formed of the yellow dye forming coupler, the magenta dye forming coupler and the cyan dye forming coupler, respectively, meet the following requirements:
110xe2x89xa7xcexmax(M)xe2x88x92xcexmax(Y)xe2x89xa795,
xe2x80x8380xe2x89xa7xcexmax(C)xe2x88x92xcexmax(M)xe2x89xa770,
0.43xe2x89xa7Abs600(M)xe2x89xa70.38,
and
0.48xe2x89xa7Abs550(C)xe2x89xa70.35,
wherein xcexmax(Y) is a wavelength at an absorption maximum of the formed yellow dye, xcexmax(M) is a wavelength at an absorption maximum of the formed magenta dye and xcexmax(C) is a wavelength at an absorption maximum of the formed cyan dye; Abs600 (M) is an absorbance at a wavelength of 600 nm of the magenta dye having 1.0 of an absorbance at the absorption maximum and Abs550 (C) is an absorbance at a wavelength of 550 nm of the cyan dye having 1.0 of an absorbance at the absorption maximum;
(4) A reflection-type or transmission-type silver halide photographic light sensitive material comprising on a refection or transmission support a blue-sensitive silver halide emulsion layer containing a yellow dye forming coupler, a green-sensitive silver halide emulsion layer containing a magenta dye forming coupler and a red-sensitive silver halide emulsion layer containing a cyan dye forming coupler, wherein spectral reflection absorption characteristics of a yellow dye, a magenta dye and a cyan dye which are formed of the yellow dye forming coupler, the magenta dye forming coupler and the cyan dye forming coupler, respectively, meet the following requirements:
108xe2x89xa7xcexmax(M)xe2x88x92xcexmax(Y)xe2x89xa7100,
80xe2x89xa7xcexmax(C)xe2x88x92xcexmax(M)xe2x89xa770,
0.42xe2x89xa7Abs600 (M)xe2x89xa70.40,
and
0.46xe2x89xa7Abs550 (C)xe2x89xa70.35,
wherein xcexmax(Y) is a wavelength at an absorption maximum of the formed yellow dye, xcexmax(M) is a wavelength at an absorption maximum of the formed magenta dye and xcexmax(C) is a wavelength at an absorption maximum of the formed cyan dye; Abs600 (M) is an absorbance at a wavelength of 600 nm of the magenta dye having 1.0 of an absorbance at the absorption maximum and Abs550 (C) is an absorbance at a wavelength of 550 nm of the cyan dye having 1.0 of an absorbance at the absorption maximum.
Thus, in the invention, a method for enhancing conflicting performances such as expanded color gamut and minimized dependency on light sources was achieved by greatly reducing the difference in wavelength at an absorption maximum between magenta and cyan dyes [i.e., xcexmax(M) and xcexmax(C)], which had been considered to cause failure in color and by specifying spectral absorptions of the magenta and cyan dyes within a narrow range.
Furthermore, preferred embodiments of the invention are as follows:
(5) The silver halide photographic material described in (3) or (4), wherein the magenta coupler is represented by the following formula (M-I) and the green-sensitive layer further containing a compound represented by the following formula (S-I) in an amount of 30 to 150% by weight, based on a total of magenta coupler(s) contained in the green-sensitive layer; the cyan coupler is represented by the following formula (C-I) and the red-sensitive layer further containing a compound represented by the following formula (S-II) in an amount of 30 to 150% by weight, based on a total of cyan coupler(s) contained in the red-sensitive layer: 
wherein R1 is a hydrogen atom or a substituent group; X is a hydrogen atom or a group capable of being released from the coupler upon coupling reaction with an oxidation product of a color developing agent (also denoted as a coupling-off group); and Z is a non-metallic atom group necessary to form a nitrogen-containing heterocyclic ring, which may be substituted by at least one substituent group;
R2xe2x80x94OHxe2x80x83xe2x80x83formula (S-I)
wherein R2 is a substituent group having 11 to 30 carbons including at least one unsaturated carbon; 
wherein R3 and R4 are each a hydrogen atom or an alkyl group; R5, R6 and R7 are each a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; Y is a hydrogen atom or a group capable of being released from the coupler upon reaction with an oxidation product of a color developing agent; 
wherein R8, R9 and R10 are each an alkyl group having 6 to 20 carbons;
(6) The silver halide photographic material described in (3) or (4), wherein the magenta coupler is represented by the foregoing formula (M-I) and the green-sensitive layer further containing a compound represented by the foregoing formula (S-I) in an amount of 30 to 150% by weight, based on a total of magenta coupler(s) contained in the green-sensitive layer; the cyan coupler is represented by the foregoing formula (C-I) and the red-sensitive layer further containing a compound represented by the foregoing formula (S-II) in an amount of 30 to 150% by weight, based on a total of cyan coupler(s) contained in the red-sensitive layer; and the yellow coupler is represented by the following formula (Y-I): 
wherein R11, is an aliphatic group or an aromaticl group; W is a 5- or 6-membered nitrogen-containing heterocyclic group capable of being released from the coupler upon reaction with an oxidation product of a color developing agent; and R12 is a ballasted aliphatic group of a ballasted aromatic group;
(7) The silver halide photographic material described in (6), wherein the magenta coupler is represented by the following formula (M-Ia) and the cyan coupler being represented by the following formula (C-Ia): 
wherein R13 is a hydrogen atom or a substituent group; R14 is a hydrogen atom or an alkyl group, a cycloalkyl group or an aryl group, each which may be substituted by at least one substituent group; Xxe2x80x2 is a hydrogen atom or a group capable of being released from the coupler upon coupling reaction with an oxidation product of a color developing agent; L is an alkylene group; and J is xe2x80x94COxe2x80x94 or xe2x80x94SO2xe2x80x94; 
wherein R15 is a hydrogen atom or an alkyl group; R16 is an alkyl group having 10 to 20 carbon atoms; and Y is a hydrogen atom or a group capable of being released from the coupler upon reaction with an oxidation product of a color developing agent;
(8) The silver halide photographic material described in (7), wherein the green-sensitive layer further contains a compound represented by formula (U-I) in an amount of 20 to 100% by weight, based on a total of magenta coupler(s) contained in the green-sensitive layer: 
wherein R17, R18 and R19 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group; R20 is a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamido group or a ureido group;
(9) The silver halide photographic material described in (8), wherein the red-sensitive layer further contains a compound represented by the foregoing formula (U-I) in an amount of 20 to 100% by weight, based on a total of cyan coupler(s) contained in the red-sensitive layer.
The yellow dyes, magenta dye and cyan dye used in the invention are dyes which have a spectral absorption maximum at the wavelength of 400 to 500 nm, 500 to 600 nm and 600 to 750 nm, respectively. The yellow dye, magenta dye and cyan dye may be comprised of a single dye or a mixture of two or more dyes.
Determination of the photographic element, transmission-type silver halide photographic material and reflection-type silver halide photographic material relating to the invention will be described. A photographic element comprising a yellow dye forming coupler, a magenta dye forming coupler and a cyan dye forming coupler; a silver halide photographic material comprising a transmission support, a yellow dye forming coupler, a magenta dye forming coupler and a cyan dye forming coupler; or a silver halide photographic material comprising a reflection support, a yellow dye forming coupler, a magenta dye forming coupler and a cyan dye forming coupler are each exposed to blue light through an optical wedge in accordance with the conventional manner and then processed with a p-phenylenediamine color developer solution to obtain a color print having a yellow wedge-wise image. A portion having 1.0 of an absorbance at the absorption maximum (xcexmax) in the obtained color print is measured with respect to spectral reflection absorption, using Color Analyzer Type 607, available from Hitachi, Ltd. From the obtained reflection absorption spectrum, the wavelength at the absorption maximum, xcexmax(Y) is determined. Similarly, exposure to green or red light and processing are conducted and from the obtained spectral absorption, xcexmax(M), xcexmax(C), Abs600(M) and Abs550(C) are determined. The photographic element, and reflection-type or transmission-type photographic material according to the invention meet the requirement of xe2x80x9cxcexmax(M)xe2x88x92xcexmax(Y)xe2x80x9d being not less than 95 and not more than 110, xe2x80x9cxcexmax(C)xe2x88x92xcexmax(M)xe2x80x9d being not less than 70 and not more than 80, Abs600 (M) being not less than 0.38 and not more than 0.43, and Abs550 (C) being not less than 0.35 and not more than 0.48; and preferably xe2x80x9cxcexmax(M)xe2x88x92xcexmax(Y)xe2x80x9d being not less than 95 and not more than 110, xe2x80x9cxcexmax(C)xe2x88x92xcexmax(M)xe2x80x9d being not less than 70 and not more than 80, Abs600 (M) being not less than 0.40 and not more than 0.42, and Abs550 (C) being not less than 0.35 and not more than 0.46.
The silver halide photographic material according to the invention is a reflection-type or transmission-type silver halide photographic material, which comprises on a reflection or transmission support at least three silver halide emulsion layer and further comprises the photographic element of the invention.
Yellow couplers used in the invention include benzoylacetoanilide-type and pivaloylacetoanilide-type couplers, as described, for example, in JP-A No. 2000-147725. Specifically, yellow couplers usable in the invention are compounds represented by the following formula (Y-I): 
wherein R11 is an aliphatic group or an aromatic group; W is a 5- or 6-membered nitrogen-containing heterocyclic group capable of being released from the coupler upon reaction with an oxidation product of a color developing agent; and R12 is a ballasted aliphatic or aromatic group.
In the formula (I), the aliphatic group represented by R11 preferably is a straight-chain, branched or cyclic alkyl group, such as methyl, ethyl, isopropyl, t-butyl, adamantly, and n-dodecyl, 1-hexylnonyl. The alkyl group represented by R1 may be substituted. Examples of substituents include a halogen atom (e.g., chlorine, bromine), an aryl group (e.g., phenyl, p-t-octylphenyl), an alkoxy group (e.g., methoxy), aryloxy (e.g., 2,4-di-t-amylphenoxy), sulfonyl group (e.g., methanesulfonyl), acylamino group (e.g., acetylamino, benzoylamino), sulfonylamino (e.g., n-dodecanesulfonyl) and hydroxy group. The aromatic group represented by R11 preferably is an aryl group having 6 to 14 carbon atoms, such as phenyl, 1-naphthyl, and 9-anthranyl. The aryl group may be substituted. Example of substituents include nitro, cyano, amino (e.g., dimethylamino, anilino), alkylthio, alkyl (as cited in the foregoing alkyl group defined by R11) and substituents (as cited in the foregoing alkyl group defined by R11). Further, R11 is more preferably an alkyl group, still more preferably branched alkyl group, and t-butyl is specifically preferred.
The ballasted aliphatic group represented by R12 is preferably a straight chain, branched or cyclic alkyl group having 8 to 21 carbon atoms, such as 2,6-dimethylcyclohexyl, 2-ethylhexyl, isotridecyl, hexadecyl, and octadecyl. The ballasted alkyl group may be via a linking group, as represented by the following formula:
xe2x80x94Jxe2x80x94Xxe2x80x94Rxe2x80x212
wherein J is a straight-chain or branched alkylene group having 1 to 20 carbon atoms, such as methylene, 1,2-ethylene, 1,1-dimethylmethylene and 1-decylmethylene; Rxe2x80x212 is a straight-chain or branched alkyl group having 1 to 20 carbon atoms, as cited in the foregoing aliphatic group represented by R11; X is a linking group, such as xe2x80x94Oxe2x80x94, xe2x80x94OCOxe2x80x94,xe2x80x94OSO2xe2x80x94, xe2x80x94COxe2x80x94, xe2x80x94COOxe2x80x94, xe2x80x94CON(R13)xe2x80x94, xe2x80x94CON(R13)SO2xe2x80x94, xe2x80x94N(R13)xe2x80x94, xe2x80x94N(R13)COxe2x80x94, xe2x80x94N(R13)SO2xe2x80x94, xe2x80x94N(R13)CON(R14)xe2x80x94, xe2x80x94N(R13)COOxe2x80x94, xe2x80x94S(O)nxe2x80x94, xe2x80x94S(O)nN(R13)xe2x80x94, and xe2x80x94S(O)nN(R13)COxe2x80x94, in which R13 and R14 are each a hydrogen atom, alkyl or aryl, as defined in the foregoing R11, and n is 0, 1 or 2. Further, Rxe2x80x212 and J may combine with each other to form a ring. The alkyl group represented by R12 may be substituted. Examples of substituents are the same as cited in the foregoing R11. The ballasted aromatic group represented by R12 is preferably an aryl group, which is the same as defined in the foregoing R11. The aryl group may be substituted. Examples of a substituent are the same as cited in the foregoing aryl group represented by R11. Of these substituents is preferred a branched alkyl group having 4 to 10 carbon atoms. Further, R12 is more preferably a ballasted aromatic group.
In the formula (Y-I), W is a 5- or 6-membered nitrogen-containing heterocyclic group capable of being released from the coupler upon reaction with an oxidation product of a color developing agent, and represented by the following formula: 
wherein Z1 is a nonmetallic atom group necessary to form a 5- or 6-membered ring, together with a nitrogen atom. Examples of the nonmetallic atom group include substituted or unsubstituted methylene or methine group, xe2x95x90Cxe2x95x90O, xe2x95x90Nxe2x80x94R15 (in which R15 is a hydrogen atom, an alkyl, cycloalkyl, aryl, or heterocyclic group), xe2x80x94Nxe2x95x90, xe2x80x94Oxe2x80x94, xe2x80x94S(O)m (in which m is 0, 1 or 2).
Exemplary examples of the compound represented by the formula (Y-I) are shown below.
Magenta couplers used in the invention include, for example, pyrazolotriazole-type couplers, as described in JP-A 2000-147725, item 2. The magenta coupler usable in the invention is preferably a compound represented by the following formula (M-I): 
wherein R1 is a hydrogen atom or a substituent; X is a hydrogen atom or a group capable of being released from the coupler upon coupling reaction with an oxidation product of a color developing agent; and Z is a non-metallic atom group necessary to form a nitrogen-containing heterocyclic ring, which may be substituted by at least one substituent group.
Representative examples of the substituent represented by R1 include an alkyl, aryl group, anilino group, acylamino and sulfonamido group, alkylthio group, arylthio group, alkenyl group and cycloalkyl group. Further are also included a halogen atom, a cycloalkenyl group, alkynyl group, heterocyclic group, sulfonyl group, sulfinyl group, phosphonyl group, acyl group, carbamoyl group, sulfamoyl group, cyano group, alkoxy group, aryloxy group, heterocyclioxy group, siloxy group, acyloxy group, carbamoyloxy group, amino group, alkylamino group, imido group, ureido group, sulfamoylamino group, alkoxycarbonyl group, arylcarbonyl group, heterocycli-thio group, spiro-compound residue and bridged hydrocarbon compound residue.
Furthermore, the magenta coupler usable in the invention is represented by the following formula (M-Ia): 
wherein R13 is a hydrogen atom or a substituent; R14 is a hydrogen atom or an alkyl group, a cycloalkyl group or an aryl group, each which may be substituted by at least one substituent group; Xxe2x80x2 is a hydrogen atom or a group capable of being released from the coupler upon coupling reaction with an oxidation product of a color developing agent; L is an alkylene group, which may be substituted; and J is xe2x80x94COxe2x80x94 or xe2x80x94SO2xe2x80x94.
Examples of the substituent represented by R13 include an alkyl group (e.g., methyl, ethyl, propyl, I-propyl, t-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, dodecyl), alkenyl group (e.g., vinyl, allyl), alkynyl group (e.g.,propargyl), aryl group (e.g., phenyl, naphthyl), heterocyclic group (e.g., pyridyl, thiazolyl, oxazolyl, imidazolyl, furyl, pyrrolyl, pyrazyl, pyrimidyl, pyridazinyl, selenazolyl, sulforanyl, piperidinyl, pyrazolyl, tetrazolyl), halogen atom (e.g., fluorine, chlorine, bromine, iodine), alkoxy group (e.g., methoxy, ethoxy, propyloxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, octyloxy, dodecyloxy), aryloxy group (e.g., phenoxy, naphthyloxy), alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl, octyloxycarbonyl, dodecyloxycarbonyl), aryloxycarbonyl group (e.g., phenoxycarbonyl, naphthoxycarbonyl), sulfonamido group (e.g., methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, hexylsulfonylamino, cyclohexylsulfonylamino, ocylsulfonylamino, dodecylsulfonylamino, phenylsulfonylamino), sulfamoyl group (e.g., aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl, butylaminosulfonyl, hexylaminosulfonyl, cyclohexylaminosulfonyl, octylaminosulfonyl, dodecylaminosulfonyl, phenylaminosulfonyl, naphthylaminosulfonyl, 2-pyridylaminosulfonyl), ureido group (e.g., methylureido, ethylureido, pentylureido, cyclohexylureido, octylureido, dodecylureido, phenylureido, naphtylureido, 2-pyridylureido), acyl group (e.g., acetyl, ethylcarbonyl, propylcarbonyl, pentylcarbonyl, cyclohexylcarbonyl, octylcarbonyl, 2-ethylhexylcarbonyl, dodecylcarbonyl, benzoyl, naphthylcarbonyl, pyridylcarbonyl), acyloxy group (e.g., acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodexylcarbonyloxy, benzoyloxy), carbamoyl group (e.g., carbamoyl, methylcarbamoyl, dimethylcarbamoyl, propylcarbamoyl, pentylcarbamoyl, cyclohexylcarbamoyl, octylcarbamoyl, 2-ethylhexylcarbamoyl, dodecylcarbamoyl, phenylcarbamoyl, phenylcarbamoyl, naphthylcarbamoyl, 2-pyridylcarbamoyl), acylamino group (e.g., methylaminocarbonyl, ethylcarbonylamino, propylaminocarbonyl, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino), sulfonyl group (e.g., methylsufonyl, ethylsulfinyl, butylsulfonyl, cyclohexylsulfonyl, 2-ethylhexylsulfonyl, dodecylsulfonyl, phenylsulfinyl, naphthylsulfonyl, 2-pyridylsulfonyl), amino group (e.g., amino, ethylamino, dimethylamino, butylamino, cyclopentylamino, 2-ethylhexylamino, dodecylamino, anilino, naphthylamino, 2-pyridylamino), cyano group, nitro group, sulfo group, carboxyl group and hydroxy group. These substituents may further be substituted by a substituent, as described above. Of these, R13 is preferably an alkyl group, alkenyl group, aryl group, acylamino group, sulfonamido group, halogen atom, heterocyclic group, sulfonyl group, acyl group, carbamoyl group, sulfamoyl group, cyano group, alkoxy group, aryloxy group, amino group, alkylamino group, ureido group, alkoxycarbonyl group, or aryloxycarbonyl group; more preferably an alkyl group; and still more preferably t-butyl.
The alkyl group represented by R14 is preferably an alkyl group having 1 to 32 carbon atoms, such as methyl, ethyl, propyl, I-propyl, t-butyl, hexyl, ocyl, dodecyl, hexadecyl, and 2-ethylhexyl. The alkyl group may be substituted by substituents, as defined in the foregoing R13. The cycloalkyl group represented by R14 is preferably a cycloalkyl group having 3 to 12 carbon atoms, such as cyclopropyl, cyclopentyl, cyclohexyl, 2-methylcyclopropyl, and adamantly. The cycloalkyl group may be substituted by substituents, as defined in the foregoing R13. The aryl group represented by R14 is preferably an aryl group having 6 to 14 carbon atoms. The aryl group may be substituted by substituents, as defined in the foregoing R13.
Examples of the group capable of being released from the coupler upon coupling reaction with an oxidation product of a color developing agent, as represented by Xxe2x80x2 include an alkoxy group (e.g., methoxy, ethoxy, propyloxy, pentyloxy, cyclopentyloxy, hexyloxy, cyclohexyloxy, octyloxy, dodecyloxy), aryl group (e.g., phenoxy, naphthoxy), heterocyclic-oxy group (e.g., pyridyloxy, thiazolyloxy, oxazolyloxy, imidazolyloxy, furyloxy, pyrrolyloxy, pyrazinyloxy, pyrimidinyloxy, pyridazinyloxy, selenazolyloxy, sulfolanyloxy, piperidynyl, pyrazolyloxy, tetrazolyloxy), acyloxy group (e.g., acetyloxy, ethylcarbonyloxy, butylcarbonyloxy, octylcarbonyloxy, dodecycarbonyloxy, phenylcarbonyloxy), sufonyloxy group, alkoxycarbonyloxy group (e.g., methoxycarbonyloxy, ethoxycarbonyloxy), aryloxycarbonyloxy group (e.g., phenyloxycarbonyloxy), alkyloxazalyloxy group, alkoxyoxalyloxy group, alkylthio group (e.g., methylthio, ethylthio), arylthio group (e.g., phenylthio, naphthylthio), heterocyclic-thio group (e.g., pyridylthio, furylthio), alkyloxythiocarbonylthio group, acylamino group (e.g., methylcarbonylamino, ethylcarbonylamino, propylcarbonylamino, pentylcarbonylamino, cyclohexylcarbonylamino, 2-ethylhexylcarbonylamino, octylcarbonylamino, dodecylcarbonylamino, phenylcarbonylamino, naphthylcarbonylamino), sulfonamido group (e.g., methylsulfonylamino, ethylsulfonylamino, butylsulfonylamino, hexylsulfonylamino, cyclohexylsulfonylamino, octylsulfonylamino, dodecylsulfonylamino, phenylsulfonylamino), N-attached nitrogen-containing heterocyclic group, alkyloxycarbonylamino group, aryloxycarbonylamino group and carboxyl group. Of the foregoing groups, a halogen atom is preferred and chlorin atom is more preferred.
The alkylene group represented by L may be substituted by substituents, as defined in the foregoing R13. Exemplary examples of the alkylene group represented by L are shown below but are not limited to these. 
L is preferably substituted or unsubstituted ethylene, and more preferably unsubstituted ethylene.
Exemplary examples of the compound represented by the formula (M-I) or (M-Ia) are shown below but are not limited to these. 
Examples of cyan couplers used in the invention include phenol-type, naphthol-type and pyrazolotriazole-type couplers. Preferred couplers are those described in JP-A 10-97039. Thus, cyan couplers usable in the invention are preferably compounds represented by the following formula (C-I): 
wherein R3 and R4 are each a hydrogen atom or an alkyl group; R5, R6 and R7 are each a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom; Y is a hydrogen atom or a group capable of being released from the coupler upon reaction with an oxidation product of a color developing agent.
Further, more preferred cyan couplers are represented by the following formulas (C-Ia): 
wherein R15 is a hydrogen atom or an alkyl group; R16 is an alkyl group having 10 to 20 carbon atoms; and Y is a hydrogen atom or a group capable of being released from the coupler upon reaction with an oxidation product of a color developing agent.
Exemplary examples of the cyan couplers represented by the formulas (C-I) and (C-Ia) are shown below but are by no means limited to these. 
formula (c-Ia)
Couplers used in the invention are used through solution in high boiling solvents, including esters such as a phthalic acid ester, phosphoric acid ester and fatty acid ester, higher saturated or unsaturated alcohols, alkylphenols, organic acid amides, ketones and hydrocarbon compounds.
Specifically, compounds represented by the following formula (S-I) or (S-II) are used as a preferred high boiling solvent usable in the invention:
R2xe2x80x94OHxe2x80x83xe2x80x83formula (S-I)
wherein R2 is a substituent group having 11 to 30 carbons including at least one unsaturated carbon; 
wherein R8, R9 and R10 are each an alkyl group having 6 to 20 carbons.
Examples of the compound represented by formulas (S-I) and (S-II) are shown below. 
To these high boiling solvents may be incorporated various photographic additives, such as an antioxidant and UV absorbent. It is known that the spectral absorption of a dye formed of a coupler varies, depending on the kind of a high boiling solvent or photographic additive, as described in JP-A No. 11-24221. In the invention, the kind of the high boiling solvent or photographic additive can be optionally selected to adjust spectral absorption characteristics of the dye. Specifically, it is preferred to use a compound represented by the following formula (U-I) in combination with couplers used in the invention: 
wherein R17, R18 and R19 are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group or an aryl group; R20 is a hydrogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamido group or a ureido group.
Exemplary examples of the compound represented by formula (U-I) are shown below.
Silver halide emulsions used in the invention can be prepared by the methods known in the art. Reflection supports used in the invention may be any material, including, for example, paper coated with polyethylene (PE) or polyethylene terephthalate, a paper support comprised of natural pulp or synthetic pulp, polyvinyl chloride sheet, polypropylene containing a white pigment, PET support and baryta paper. Of these is preferred a support having water-proof resin coat on both sides of base paper. The water-proof resin is preferably PE, PET or copolymers thereof.
Transmission supports used in the invention may be any material, including, for example, homopolymers such as polyesters (e.g., polyethylene terephthalate), polyvinyl alcohol, polyvinyl chloride, fluorovinyl resin and polyvinyl acetate and their copolymers; homopolymers such as cellulose acetate, polyacrylonitrile, poly(alkyl acrylate), poly(alkyl methacrylate), polymethacrylate, poly(alkyl vinyl ester), poly(alkyl vinyl ether) and polyamide, and their copolymers. Of these, polyesters are preferred. The polyesters include not only thermoplastic resins comprised of a polyester alone but also those which contain other polymers or addenda within the range of causing no variation in practical characteristics of the polyester resin as a main component.
The present invention are applied preferably to photographic materials forming images for direct appreciation, and examples thereof include color paper, color reversal paper, positive image forming photographic material, photographic material for use in display and photographic material for use in color proof.